4-Methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxy → 1-(5,6-dichloro-1H-benzoimidazol-2-yl)-2,2,2-trifluoro-ethanone

HRID 2043300Notes

Reaction equation

HRID 2043300 reaction equation
[Cl:1][C:2]1[C:16]([Cl:17])=[CH:15][C:5]2[NH:6][C:7]([CH:9]([OH:14])[C:10]([F:13])([F:12])[F:11])=[N:8][C:4]=2[CH:3]=1.CC1(C)N([O-])C(C)(C)CC(OC)C1.[Br-].[K+].Cl[O-].[Na+]>C1COCC1.O.C(OCC)(=O)C>[Cl:17][C:16]1[C:2]([Cl:1])=[CH:3][C:4]2[NH:8][C:7]([C:9](=[O:14])[C:10]([F:13])([F:11])[F:12])=[N:6][C:5]=2[CH:15]=1

Participants

8

Reactant 4

HCID 1253234-Methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyHCID 253877Potassium BromideHCID 116377781-(5,6-dichloro-1H-benzoimidazol-2-yl)-2,2,2-trifluoro-ethanolHCID 23665760Sodium Hypochlorite

Product 1

HCID 115943701-(5,6-dichloro-1H-benzoimidazol-2-yl)-2,2,2-trifluoro-ethanone

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

1-(5,6-Dichloro-1H-benzoimidazol-2-yl)-2,2,2-trifluoro-ethanol (0.29 g; 1.00 mmole), 4-methoxy-2,2,6,6-tetramethyl-1-piperidinyloxy free radical (4-methoxy-TEMPO free radical; 4.4 mg; 0.03 mmoles) and potassium bromide (KBr; 13 mg; 0.11 mmoles) were dissolved in THF (2.9 mL). The reaction mixture was stirred while cooled to −10° C., after 10 min. a sodium hypochlorite solution (bleach; 10-13% aqueous; 2.10 mL; 3.53 mmoles) was added and allowed to stir for 15 min., then warmed to room temperature and stirred for 15 min. The reaction mixture was diluted with water (20 mL) and ethyl acetate (30 mL), the layers were separated and the aqueous layer was extracted with ethyl acetate (3×30 mL). The extracts were combined and washed with water (30 mL) and brine (40 mL), then dried over Na2SO4. The filtrate was concentrated in vacuo and purified by column chromatography (SiO2; 100% ether) to yield the title compound as a light yellow solid.

Workup

  1. additionwas added
  2. stirringto stir for 15 min.
  3. stirringstirred for 15 min
  4. customthe layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate (3×30 mL)
  6. washwashed with water (30 mL) and brine (40 mL)
  7. dry with materialdried over Na2SO4
  8. concentrationThe filtrate was concentrated in vacuo
  9. custompurified by column chromatography (SiO2; 100% ether)

Sources & evidence

ORD record
ord-31fa3cc1582e4c8183bab6d955da9326
Source dataset
uspto-grants-2013_11
Patent number
US08586616B2

Reaction notes

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